Method of producing artificial resin



May 15, 1928. 1,669,831

C. KULAS METHOD 0F PRODUCING ARTIFICIAL RESIN F'iied oct. 16, 1925 ELMea fe d 1go oled vwwtcoi A Carl Kulas M5, Mio/M Raw mai-erm] PatentedMay 15, 1928.

[PATENT oF CARL IULM, 0l' LEIPZIG, GmANY.

wel Fica@l METHOD 0l' PEGITUGIIN'G' ARTIFICIAL um.

appiicgtioii ned' october is, 192s. semi no. casas.

My invention relates to a method of manufacturing artificial resin fromsuch constituents as phenolic-formaldehyde condensation roducts, tar,crude tar oils, crude methyls HaOI-I vand the like.

'The principal object of m invention is to provide a continuous methofor producing artificial resin in sheet or leaf form, especiallysuitable for preparing shellac or lacuei'. i q Briefly stated, themethod consists in reacting the constituents of the resin in the resenceof heat, then cooling and settling to Ering about the formation of astratum of tacky resin and a liquid stratum, subjecting the tacky resinstratum to a cold li uid removal action, preferably centri thereuponsubjecting the partially ehydrated resin `to an eva orating andconcentrating action, preferab `y by rapid motion o'n the periphery of aheated drum, and finally cooling and setting the resin, desirably on.the periphery of a cooled drum, whence it is removed in desired leaf orsheetform. The liquid stratum may have its resin content drawn oif andsubjected to the treatment described above with respect to the Atackyresin stratum.

The preferred apparatus for practicing the method includes a reactionvessel, tanks into which the resin stratum and liquid stratum arerespectively drawn, a centrifugal'apparatus with which the tankscommunicate, and a battery of rotary drums, hot and cool, to which theproduct successively passes. Suitable means are provided for regulatingthe thickness ofthe layer of material taken up by the drums, and forstripping the product from the drums. V

Artificial resin is usually placed on the market in the form of blocks,pieces, grains or powder. In the manufacture of the resin, theconstituents, which usually consist of phenol-formaldehyde with orwithout reaction accelerators and with or'without the ade dition ofnatural or artificial resin, are combined in a closed cookm distillingapparatus. he liquid "which Vseparates out is removed by distillationfrom resin thus produced, aft-er cooling and setting, is generally inthe form of blocks or large pieces, and to render'it available forugially,

(or boiling) and use as a lacquer or shellac', so as to be-s'oluble inthe usual artificial resin solvents, the blocks or pieces must undergo atime conv suming comminuting and pulverizing action'` which causes veryconsiderable mechanical4 `diliculty.

The comminuting and pulverizing action is particularly diiiicult in thecase of resits, i. e., those artificial resins which by reason .of theirinsolube and unmeltable iinal condition are extremely susceptible toheat. The meltin point of the resit in its resol stage is or in'arilyverylow (about 50 degrecs Celsius), and in the resol stage theseproducts tend to become sticky or tacky as the result of the frictionalheat developed by the guiding or comminuting mechanism.

As aconsequencepof the increased tem era.

ture the resol undesrably changes its c eme. ical condition b thefurther reaction of the constituents, being convertedv into the resitolori'esit stage, in which it gums the grindin .mechanism and causesstoppage thereo The necessary consequences are loss ottime, material andmoney.-.

The process ordinarily employed for melt#- in natural resins is not,applicable to artilicial resins because, despite their otherwise highlydesirable properties, they are subject to chemical .changes in thepresence of heat, i. e., they are changed into resitol and resit,

which can only be treated in small quantities V without substantialloss, and become prac.

tically useless if it be attempted to treat large quantities at a time.

The production methods heretofore em ployed were always'of anintermittent, very limited, character, in that the quantities ofconstituents necessary to produce a given uantity of final product wereplaced intot e reaction vessel, and upon completion of the product allthe steps of the method were necessarily repeated if a new quantity ofresin was to be produced.

By the use of the installation, shown schematically in. the accompanyingdrawing, artificial resin may be produced by an automatic, continuousmethod.

The required quantities of raw materials for reducing a given yield andquality of arti cial resin are placed into-the reaction vesel 1 which issubjected to heat until `the desired reaction has taken place. Aftercompletion of the reaction the contents of the vessel are permitted tostand and cool until.

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they separate into two strata. The upper 4 `rwatery stratum issubstantially free ofresin, while the lower stratum consists of tackyresin (resol or novolack dependent upon the character of theconstituents employed) containing about 15 to 20 percentum of liquid.

The bottom of the\ vessel 1 is provided with valve mechanism 2 whichcontrols the inflow' of the contents of the vessel 1 into pipes 3 and 4leading, respectivel to the tanks or receptacles 5 and 6. he resinstratum is drawn from vessel 1 through pipe 3 to the tank 5 and thewatery stratum is drawn into the tank 6. If desired, the vessel 1 may berecharged with anew sup ly of resin constitutents, and the latter boi edand caused to react inthe same manner as theA preceding charge.VVhile-the reaction is progressing the other phases of the method aretaking place, and the method is thus a continuous one in the true senseof the term.

The tanks 5 and,6 are connectedto a centrifugal apparatus 7 by means ofpipes 8 and 9, controlled by the valves 10 and 11, respectively. Thecentrifugal apparatus 7 may be of any approved type. The tacky resin isconducted from tank 5 to the centrifugal ap aratus 7 where it is freed,by cold centrl ugal action, of about 10 percentum of its liquid content.

Leading from the bottom of the centrifugal apparatus 7 is a pipe 12which communicates, through a valve 13, with a. receiving vat 14 throughits upper wall. The resin, after treatmentin the centrifugal apparatus7, passes from the latter. through the pipe 12 into the vat 14.

The resin next passes to a battery of hot and cold drums, to bevaporized, concentrated, cooled and set. A plurality of both hot andcold drums may be employed, but in the drawing I have shown but one hotand one cold drum 'as these will suffice` to make the principle of theinvention clear.

Connected to the base of the vat 14 is a pipe 15, having a valve 16therein, said ipe communicating with a trough 17 whic is closelyjuxtaposed to and extends along the entire width of the periphery of aheated drum 18. The drum 18 which is made of metal, such as iron,copper, nickel, aluminum or the like, is hollow and is so constructed asto be heated .interiorly or exteriorly by suitable means (not shown).Adjacentto, but spaced from the drum 18, with lts shaft parallel to thatof the drum 18, is a second hollow, metallic drum 19, which may beinteriorly or exteriorly cooled by suitable means (not shown). The drumsare rotated by means of belts 20 and 21 from a power yshaft 22.

The resin from vat 14 passesthrough pi e i 15 into the trough 17 to betaken up by t e periphery of the heated drum 18 and to be carried aroundthereon. For artificial resins which are not susceptible to heat, i. e.,those which behave like natural resins, such as novolack and otherpermanently soluble artificial resins, the battery of drums need consistof but one heated drum and one cooled drum, but for the production ofresits it is advantageous to employ a series of heated drums, the numberused depending on the character and quantity of the roduct beingmanufactured, and if desired t e drums may be graduated as totemperature. Ordinarily but one cooling drum 1s necessary, irres ectiveof the number of heating drums w ich are used.

Arranged immediatel above the trough 17 is a doctor blade 23, a justabletoward and from the periphery of the drum 18, whereby the thickness ofthe layer of resin taken up by the drum 18 may be regulated. Closelyadjacent the drum 18 at what may be termed its discharge side, oppositethe blade 23, is a fixed blade or stri per 24 the function of which isto remove om the drum the resin adhering thereto. This resin falls intoa trough 25 between and Iin immediate proximity to both drums 18 and 19.Above the trough 25 is an adjustable doctor blade 26 to regulate thethickness of the layer of resin taken up on the periphery of the coolingdrum 19, and at the discharge side of drum 19, opposite the blade 26 isa fixed blade or stripper 27 to remove from the periphery of 1s timedrum 19 the resin which has by t cooled and set.

The blades 23, 24, 26 and 27 are the full width of the drums 18 and 19and act across the entire transverse peripheral surfaces thereof. Whenthe resin reaches the blade 27 it is stri ped from the drum in sheets ofany desiredpthinness, and usually comes 0H in the form of scales orleaves, which fall into the rece tacle 28 whence they may be conveyed tot e acking and shipping room, or to any other esired place.

By permitting the contents of the tank 6 to stand for a tain quantity oresin will settle which may be passed through the several stages of themethod described with respect to the resin in tank 5. To the liquidwhich remains in tank 5 I add new uantities of raw materials, and thencon uct the mass to the reaction vessel 1 to be used anew. After hav-.ing been used twice the liquid from tank 5 is discharged as not furtherusable.

The drawing shows a complete o erating installation, and in addition tot e parts heretofore described, the 1installation also desirablyincludes the following z-Tank cars 29 and 30 in which the raw materialsare conveyed to the plant; pumps 31 and 32 by means of which the rawmaterials are raised from the tank cars through the pipes 33 and 34 intothe stora e vets 35 and 36; storage tanks 37 and 38 igor acids, alkalisetc., measroper length of time a cer-- 'zal Alas

uring means 39 to 42 for re ating the tiow of raw materials, acids analkalis into the reaction vessel 1; a foam catcher 43 for vessel 1, anda reflux cooler 44 for vessel 1.

The heated drums (drum 18 in the drawing) are preferably covered by ahousing 45 connected b a pipe-16 withan exhaust fan 47 which rawsK oilthe fumes or vapors which may be condensed and used as or converted intodisinfectants and the like.

lThe invention, described above, has many advantages over existingpractice and results in a notable improvement in the quality of theresin produced. According to present manufacturing methods, which arelong and expensive, there is a complete lack of uniformity as tocharacter and quality ofthe resultlng product because close control ofthe process is impossible due to the long period of distillation and thelarge quantities of raw materials used. To operate economicallyby theold method, it was necessary to' employ large quantities of rawmaterials which during distillation were ver active and unruly, foamedviolently an deposited resin on the cooling apparatus, so that becauseof the failure of proper cooling action excess pressure and spontaneousheating of the resin occurred. These conditions became particularlydangerous shortly before completion of the distillation process, becauseat that stage the resols would shortly change into resitol or resit andwould then be useless for the further steps of the process. By means ofthe present invention all losses of this kind are precluded, inasmuch asthe entire procedure can be supervised very easily by a single skilledworkman.

There need be no limit to the magnitude of o eration, the output beingmerely depen enton the dimensions of the installation.

In the methods as heretofore practiced, the liquid residue was a sourceof considerable trouble and because of its content of 'small quantitiesof resin, phenol, formaldehyde, catalyst etc., its removal was ditlicultas well as entailing a loss of valuable material. According to mymethod, by which the liquid from tank 6 has its valuable contents'extractedx and is then reused, the trouble and loss in this respect areentirely eliminated.v

A further ve important advantage of my method lies 1n the fact that, incase of any operating disturbances or unavoidable sto page of operationdue to lack of power, lig t, steam or heat, the process may be stoppedwithout an serious consequences by simply closing o the iow passages;the resulting product will not be detrimentally affected, and when thedisturbance has ceased the process may quickly be resumed.V This is insharp -distinction to present practice duced by the new method is muchsuperior to that produced b 'other methods because the resin on the surace of the heated drums, in my method, can be subjected to much highertemperatures, without detriment, than a strongly reactin'g large' bodyof resin (of several hundred pounds) in a closed distilling vessel, andalso because the evaporation of the impurities in the mass is much moreintense and thorough .in my method than it is in a methode-mployin aclosed distilling vessel having a' constant y decreasing vaporizingsurface in relationto the entire body of resin. l

It should also be noted that the artificial resin produced in accordancewith my invention has a much higher melting point than a correspondinresin produced with the use of a closed istillation vessel. The

odor of carbolic acid and formalin always present in resins of the oldty e is almostentirely absent from my p uct, due to the intenseevaporating action to which the resin is subjected on the heated drum.

4 Furthermore, the caking and sticking at ordinary room temperature, soprevalent in resins heretofore manufactured is entirely eliminated in myproduct, and the latter, even afterlying for a long time, may be quicklyand completely dissolved in the appropriate solvents. v

In consequence of the complete elimination, by my method, of all'undesirable voIa-. tile and fluid constituents, I am not limited to theuse of only phenol-formaldehyde condensationproducts in the productionof artiicial resin, but I may also employ tar, crude tar oils, crudemethyl CHSOH andl the like as the initial substances.

I claim 1. The herein described vmethod of manufacturing artificialresin of the phenolformaldehyde type, which consists in reactingtheresin constituents in the presence of heat, cooling and settling theresulting product to form a liquid stratum anda-partially dehydratedresin stratum, subjecting the resin stratum to cold centrifu al action,thereafter subjecting successive t in. layers of the resin to rotationwhile supported on a heated surface, and finally subjecting said layersto rotation while supported on a cool surface.

2. The herein described method of manufacturing artificial resin of thephenolformaldehyde type, which consists in reacting the resinconstituents in the presence of heat, cooling andusettling the resulting,product to form a lower stratum of substantially dehydrated resin andan upper stratum of liquid, subjecting the resin to cold centrifugalaction, thereafter impartin rapid motion to the resin in the presence oheat, then rapidly moving the resin in a cooling atmosphere, and finallyforming the resin into desired shape. v

3. The herein described method of manuacturing `artificial resin of thephenolformaldehyde type, which consists in reacting the resinconstituents in the presence of heat, cooling and settling the resultingproduct to form a lower stratum of substantially dehydrated resin and anupper stratum of liquid, subjecting the resin to cold centrifugal actionto eliminate the major portion of its liquid content, then subjectingsuccessive thin layers of the resin to rotation while supported on aheated surface, thereafter subjecting said layers to rotation Whilesupported on a cooled surface, and finally stripping said layers insheet form from the last mentioned surface.

4. The herein described method of manufacturing artificial resin` oftheV phenolformaldehyde type, which consists in reacting the resinconstituents in a closed container in the presence of heat, cooling andsettling the resulting product to form a lower stratum of substantiallydehydrated resin and an upper stratum of liquid containing a relativelysmall quantity of resin, extracting the resin from the liquid stratum,and subjecting said resin successively to cold centrifugal action, rapidrotation lin the presence of heat and rapid rotation in a coolingatmosphere.

5. The herein described method of manufacturing artificial resin of thephenolformaldehyde type, which consists in reacting the resinconstituents in the presence of heat, cooling and settling the resultingproduct to form a lower stratum of substantially dehydrated resin and anupper stratum of liquid containing a relatively small quantity of resin,permitting the resin in the liquid to settle and combining the settledresin with that of the resin stratum, subjecting the entire body ofresin to cold centrifugal action, then subjecting the resin to rotationin the presence of heat, and finally rotating the resin in a coolingatmos here.

In testimony whereo I have affixed my signature.

C i. 1,- `s KULAS.

